EP2276562B1 - Utilisation d'un catalyseur supporté contenant des métaux précieux pour la déshydrogénation oxydative - Google Patents

Utilisation d'un catalyseur supporté contenant des métaux précieux pour la déshydrogénation oxydative Download PDF

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EP2276562B1
EP2276562B1 EP09723248.2A EP09723248A EP2276562B1 EP 2276562 B1 EP2276562 B1 EP 2276562B1 EP 09723248 A EP09723248 A EP 09723248A EP 2276562 B1 EP2276562 B1 EP 2276562B1
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silver
sparingly soluble
silver compound
catalyst
supported
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EP2276562A1 (fr
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Torsten Mäurer
Georg Seeber
Radwan Abdallah
Thorsten Johann
Günter WEGNER
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BASF SE
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BASF SE
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0219—Coating the coating containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/76—Dehydrogenation
    • B01J2231/763—Dehydrogenation of -CH-XH (X= O, NH/N, S) to -C=X or -CX triple bond species
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/007—Mixed salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/17—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid

Definitions

  • the present invention relates to the use of a supported silver-containing catalyst for the preparation of olefinically unsaturated carbonyl compounds from olefinically unsaturated alcohols by oxidative dehydrogenation and corresponding supported silver-containing Katalsysatoren.
  • the present invention relates to the use of supported silver catalyst obtainable by a particular method for the preparation of 3-methylbut-2-en-1-al from 3-methylbut-3-en-1-ol.
  • EP-A 881,206 describes a process for the continuous industrial production of unsaturated aliphatic aldehydes in a shell-and-tube reactor.
  • Preferred catalysts for this process are silver-supported catalysts which consist of inert carrier spheres containing from 0.1 to 20% by weight, based on the amount of carrier, of a layer of metallic silver in the form of a smooth, abrasion-resistant Shell are coated. Furthermore, a specific ratio of the largest diameter of the coated catalyst balls to the inner diameter of the reaction tube should preferably be maintained.
  • the catalysts used in this process are silver catalysts wherein the silver is supported on a porous refractory support having a certain BET specific surface area.
  • the silver can be applied to the support as a suspension of silver or silver oxide in a liquid medium, for example water, or by impregnation of the support with a solution of a silver compound. Subsequently, this silver compound is reduced to elemental silver by thermal treatment.
  • prenal 3-methylbut-2-en-1-al is an important precursor to citral, which in turn is an important product for a variety of chemical syntheses.
  • the catalysts described in the literature for the production of prenal (3-methylbut-2-en-1-al) are prepared by relatively complex processes and under production conditions which are in need of improvement. It would therefore be desirable to obtain noble metal-containing supported catalysts for the synthesis of prenal from isoprenol (3-methylbut-3-en-1-ol), which are accessible in a simple manner and are also controlled in terms of their selectivity simply by additions of promoters acting as promoters can.
  • this object is achieved by the use according to claim 1 for the preparation of olefinically unsaturated carbonyl compounds from olefinically unsaturated alcohols by oxidative dehydrogenation.
  • the present invention further relates to a process for the preparation of a supported silver-containing catalyst for the oxidative dehydrogenation of olefinically unsaturated alcohols according to claim 4.
  • the present invention relates to supported silver-containing catalysts according to claim 6.
  • the specific resistance is determined in a measuring cell whose bottom consists of stainless steel and whose sheath is made of insulating plastic (inner diameter 10 mm, height 32 cm, catalyst volume about 25 ml).
  • the catalyst is charged and shaken a little to achieve a uniform catalyst bed. Thereafter, a stainless steel punch is placed on the catalyst bed.
  • the stamp and the bottom serve as measuring electrodes in this measuring arrangement.
  • an ammeter is connected in series with the sample and a voltage of between 10 mV and 5 V is set with a power supply. The associated current is registered and the resistivity is calculated.
  • the measurement is carried out at atmospheric pressure and a humidity of max. 50% at a temperature in the range of 22 - 25 ° C performed.
  • a supported silver-containing catalyst is used, which is obtainable by applying a complexed sparingly soluble silver compound, optionally in admixture with additives acting as promoters, from suspension or solution to steatite as support material.
  • the silver compound is present in the suspensions or solutions from which it is applied in complexed form to steatite as support material, preferably in proportions, calculated as noble metal, in the range from 0.5 to 50% by weight, preferably in the range from 1 to 40% by weight. %, and more preferably in the range of 5 to 35% by weight.
  • all silver compounds which in aqueous solution at a temperature of 25 ° C. and a pH of 7 are suitable for a solubility of less than 5.0 g / l, more preferably less than 1 g / l and particularly preferably less than 0.5 g / l.
  • salts of silver with saturated or unsaturated mono-carboxylic acids such as. As formic acid, acetic acid, propionic acid, butyric acid, lactic acid or salts of benzoic acid or salicylic acid called.
  • compounds of saturated or unsaturated di-carboxylic acids such as fumaric acid or maleic acid or of saturated or unsaturated tri-carboxylic acids such as.
  • citric acid or its salts As mentioned above, all sparingly soluble compounds of the noble metals are suitable, so that the above enumeration is to be understood only as an example enumeration.
  • the sparingly soluble silver compounds are brought into contact as solids with complexing agents or solutions of complexing agents.
  • Complexing agents according to the invention are amine, hydroxy and or thio macrocycles.
  • oxalates in particular silver oxalate, are used as sparingly soluble salts.
  • the sparingly soluble silver compounds are brought as a solid with the complexing agent or a solution of the complexing agent in contact, whereby a complexed solution or suspension of the sparingly soluble silver compound is formed.
  • This suspension or solution of the sparingly soluble silver compounds may be added as promoters suitable further additives.
  • alkali, alkaline earth and transition metals such as Li, Rb, Cs, Ca, Mg, V, Co, Ni, Ir or Re
  • halides fluorides, chlorides
  • Sulfur-containing anions such as sulfates, sulfites or sulfides can be used.
  • phosphates, cyanides and hydroxides and carbonates or mixtures thereof are also possible to use anions of heteropolyacids, in particular heteropolyacids of the elements of the sixth and seventh subgroups of the periodic table (notation according to the 1985 IUPAC proposal).
  • the complexed silver compound of suspension or solution which optionally may contain promoters as stated above, is applied to steatite as a suitable carrier material.
  • the support materials are as little as possible porous and have a BET surface area of not more than 0.1 m 2 / g.
  • the carrier materials are spherical and have an average diameter of 1.3 to 2.5 mm.
  • the inventive carrier material is steatite, a ceramic material based on natural raw materials, which consists of the main component soapstone (Mg (Si 4 O 10 ) (OH) 2 ), a natural magnesium silicate. Furthermore, additives of clay and feldspar or barium carbonate may be included.
  • the noble metal itself is formed on the surface of the support material of the silver compound, which then constitutes the active species of the supported catalyst.
  • the silver contents, measured in% by weight, based on the support material, after the thermal treatment are generally in the range from 0.2 to 25% by weight, preferably in the range from 0.5 to 20% by weight, and particularly preferably in the range of 1 to 15 wt .-%.
  • any silver salts for example silver nitrate or others Silver salts such.
  • silver sulfate, silver fluoride, silver triflate, silver perchlorate or tricyanoargentate or tricyanoargentate compounds are used.
  • silver starting materials such as silver chloride, silver bromide or silver iodide, silver sulfite or silver carbonate, which by suitable treatment with acids such.
  • acids such as hydrogen fluoride, nitric acid or sulfuric acid can be brought into solution.
  • solutions of these salts of the silver compounds can then be combined with precipitating agents in dissolved form to precipitate the sparingly soluble silver compound.
  • both the precipitation reagent can be added to the silver solution, as well as the solution of the silver salt to the precipitating reagent.
  • the precipitating agent can be diluted in solid or liquid form or used undiluted.
  • precipitation reagents can be used oxalic acid or its salts, which is particularly preferred, saturated or unsaturated mono-carboxylic acids such as formic acid or its salts, acetic acid or its salts, propionic acid or its salts, butyric acid or its salts or lactic acid or its salts.
  • benzoic acid and benzoeates and salicylic acid and its salts are also suitable.
  • saturated or unsaturated dicarboxylic acids such as fumaric acid and its salts (fumarates) and maleic acid and its salts (maleinates).
  • saturated or unsaturated tri-carboxylic acids such as. As citric acid or salts thereof called.
  • the sparingly soluble silver compounds can be isolated from the solution by filtration, filtration through suction filters or other suitable methods and immediately thereafter be brought into contact with the complexing agent.
  • This procedure has advantages in the case of poorly soluble silver compounds which have a certain instability or involve risks in their handling.
  • the previous in situ preparation of the oxalate is particularly preferred.
  • the supported silver-containing catalysts obtainable by the above procedure can be used particularly advantageously for the preparation of 3-methylbut-2-en-1-al from 3-methylbut-3-en-1-ol.
  • the product is also known by the common name prenal, the starting material under the common name isoprenol.
  • the reaction is preferably carried out in a shell-and-tube reactor, as described, for example, in US Pat. B. in the EP-A 881,206 is described performed.
  • a shell-and-tube reactor as described, for example, in US Pat. B.
  • the EP-A 881,206 is described performed.
  • the desired reaction product is separated from unreacted educt by distillation in a first stage.
  • an azeotrope which consists of 70% of 3-methylbut-3-en-1-al and 30% of 3-methylbut-2-en-1-al. The latter is, as mentioned above, the thermodynamically favored product.
  • Prenal can be transformed into good Yield can be produced at lower temperatures and with good selectivity from isoprenol.
  • Fig. 1 shows the selectivity as a function of isoprenol conversion and Fig. 2 the isoprenol conversion as a function of temperature.
  • Steatite spheres with a diameter of 1.5 to 1.8 mm were wetted by applying a solution of silver oxalate complexed with ethylenediamine.
  • the steatite beads thus wetted with the silver solution were then treated in airflow at 280 ° C for 12 minutes.
  • the specific resistance of the catalyst thus obtained was 5 m ⁇ * m.
  • the catalyst thus obtained was tested in the experimental plant from Example 1 for its catalytic effect.
  • the same bed height and the same throughput of isoprenol and air were used as in Example 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (7)

  1. Utilisation d'un catalyseur supporté, contenant de l'argent, pouvant être obtenu par
    a) application d'un composé à base d'argent, complexé, peu soluble, à partir d'une suspension ou d'une solution sur de la stéatite comme matériau support,
    b) traitement thermique consécutif du produit obtenu après l'étape a) à des températures dans la plage de 100 à 400°C sur une période de 5 min à 5 h,
    le métal noble élémentaire étant obtenu par réduction à partir du composé à base d'argent,
    pour la préparation de composés carbonyle oléfiniquement insaturés à partir d'alcools oléfiniquement insaturés par déshydrogénation oxydante,
    les complexants étant des hydrocarbures contenant des groupes amine, hydroxy et carboxyle, l'ammoniaque ou des macrocycles à fonction oxo, aza ou thio et
    des composés d'argent présentant une solubilité en solution aqueuse, à une température de 25°C et à un pH de 7, inférieure à 5,0 g/l étant utilisés comme composés à base d'argent peu solubles.
  2. Utilisation selon la revendication 1, caractérisée en ce que le composé à base d'argent est appliqué en mélange avec des additifs agissant comme promoteurs.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que du 3-méthylbut-2-én-1-al est préparé à partir de 3-méthylbut-3-én-1-ol.
  4. Procédé pour la préparation d'un catalyseur contenant de l'argent, supporté, pour la déshydrogénation oxydante d'alcools oléfiniquement insaturés, caractérisé en ce que
    a) un composé à base d'argent, complexé, peu soluble, est appliqué à partir d'une suspension ou d'une solution sur de la stéatite comme matériau support et ensuite
    b) le produit obtenu dans l'étape a) est traité thermiquement à des températures dans la plage de 100 à 400°C sur une période de 5 min à 5 h,
    le métal noble élémentaire étant obtenu par réduction à partir du composé à base d'argent,
    les complexants étant des hydrocarbures contenant des groupes amine, hydroxy et carboxyle, l'ammoniaque ou des macrocycles à fonction oxo, aza ou thio et
    des composés d'argent présentant une solubilité en solution aqueuse, à une température de 25°C et à un pH de 7, inférieure à 5,0 g/l étant utilisés comme composés à base d'argent peu solubles.
  5. Procédé selon la revendication 4, caractérisé en ce que le composé à base d'argent est appliqué en mélange avec des additifs agissant comme promoteurs.
  6. Catalyseur supporté contenant de l'argent, présentant une résistance spécifique qui n'est pas supérieure à 1000 mΩ∗m, pouvant être obtenu par
    a) application d'un composé à base d'argent, complexé, peu soluble, à partir d'une suspension ou d'une solution sur de la stéatite comme matériau support,
    b) traitement thermique consécutif du produit obtenu après l'étape a) à des températures dans la plage de 100 à 400°C sur une période de 5 min à 5 h,
    le métal noble élémentaire étant obtenu par réduction à partir du composé à base d'argent,
    les complexants étant des hydrocarbures contenant des groupes amine, hydroxy et carboxyle, l'ammoniaque ou des macrocycles à fonction oxo, aza ou thio et
    des composés d'argent présentant une solubilité en solution aqueuse, à une température de 25°C et à un pH de 7, inférieure à 5,0 g/l étant utilisés comme composés à base d'argent peu solubles.
  7. Catalyseur supporté contenant de l'argent selon la revendication 6, caractérisé en ce que le composé à base d'argent est appliqué en mélange avec des additifs agissant comme promoteurs.
EP09723248.2A 2008-03-19 2009-03-16 Utilisation d'un catalyseur supporté contenant des métaux précieux pour la déshydrogénation oxydative Active EP2276562B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008014910A DE102008014910A1 (de) 2008-03-19 2008-03-19 Verwendung eines geträgerten edelmetallhaltigen Katalysators zur oxidativen Dehydrierung
PCT/EP2009/053081 WO2009115492A1 (fr) 2008-03-19 2009-03-16 Utilisation d'un catalyseur supporté contenant des métaux précieux pour la déshydrogénation oxydative

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EP2276562A1 EP2276562A1 (fr) 2011-01-26
EP2276562B1 true EP2276562B1 (fr) 2019-06-26

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US (1) US8779212B2 (fr)
EP (1) EP2276562B1 (fr)
JP (1) JP5745393B2 (fr)
CN (1) CN101977684B (fr)
DE (1) DE102008014910A1 (fr)
DK (1) DK2276562T3 (fr)
ES (1) ES2746179T3 (fr)
WO (1) WO2009115492A1 (fr)

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US8680340B2 (en) 2011-04-28 2014-03-25 Basf Se Precious metal catalysts with low metal loading for oxidative dehydrogenations
MX2013012389A (es) 2011-04-28 2013-11-04 Basf Se Catalizadores de metales nobles con baja carga de metal de la deshidrogenaciones oxidativas.
CN103285902B (zh) * 2012-02-29 2015-06-24 北京安耐吉能源工程技术有限公司 脱氢催化剂及其制备方法和应用以及环己醇脱氢制备环己酮的方法
CN103285906B (zh) * 2012-02-29 2015-06-24 北京安耐吉能源工程技术有限公司 脱氢催化剂及其制备方法和应用以及环己醇脱氢制备环己酮的方法
US9186655B2 (en) 2012-06-15 2015-11-17 Allen L. Johnson Metal eutectic supported metal catalyst system and reactions with the metal catalyst system
MX2015001492A (es) 2012-08-01 2015-04-08 Basf Se Catalizador que comprende un metal noble soportado para la epoxidacion o deshidrogenacion oxidativa.
RU2674990C1 (ru) * 2013-12-19 2018-12-14 Сайентифик Дизайн Компани, Инк. Высококонцентрированные серебросодержащие растворы для изготовления катализаторов синтеза этиленоксида
CN103980241B (zh) * 2014-04-23 2015-10-21 迈奇化学股份有限公司 一种δ-戊内酯的生产方法
CN109422632B (zh) * 2017-08-28 2021-11-09 中国科学院大连化学物理研究所 一种催化氧化异戊烯醇制异戊烯醛的方法
CN107812531B (zh) * 2017-10-19 2020-06-16 万华化学集团股份有限公司 一种烯属不饱和醇制备烯属不饱和醛的催化剂、其制备方法及其用途
CN108014797B (zh) * 2017-12-08 2020-08-28 万华化学集团股份有限公司 一种用于不饱和多碳醇氧化的负载型银单原子催化剂及其制备方法
CN108452799B (zh) * 2018-05-10 2021-06-22 北京化工大学 一种负载型银催化剂的制备方法及其催化苯甲醇无氧脱氢制苯甲醛的应用
WO2020099390A1 (fr) 2018-11-13 2020-05-22 Basf Se Lit de catalyseur comprenant des corps de catalyseur d'argent et processus de déshydrogénation oxydative d'alcools à insaturation oléfinique
CN111298808B (zh) * 2020-04-02 2022-07-12 万华化学集团股份有限公司 一种核壳型催化剂的制备方法和应用
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DE102008014910A1 (de) 2009-09-24
US20110015446A1 (en) 2011-01-20
JP2011515361A (ja) 2011-05-19
EP2276562A1 (fr) 2011-01-26
WO2009115492A1 (fr) 2009-09-24
JP5745393B2 (ja) 2015-07-08
CN101977684B (zh) 2013-07-10
DK2276562T3 (da) 2019-09-23
US8779212B2 (en) 2014-07-15
ES2746179T3 (es) 2020-03-05
CN101977684A (zh) 2011-02-16

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